K. Štamberg

Evaluation of polyacrylonitrile (PAN) as a binding polymer for absorbers used to treat liquid radioactive wastes

The chemical and radiation stability of polyacrylonitrile (PAN) in the form of beads (B-PAN), similar to the beads of composite absorbers, and one selected composite absorber (ammonium molybdophosphate, the active component in PAN binder [AMP-PAN], a prospective candidate for the treatment of acidic wastes) were studied. Aqueous 1M HNO{sub 3} + 1M NaNO{sub 3}, 1M NaOH + 1M NaNO{sub 3}, and 1M NaOH were chosen as simulants of DOE acidic and alkaline wastes. In addition,radiation stability was determined indistilled water. The chemical stability of B-PAN and AMP-PAN beads was tested for a period up to one month of contact with the solution at ambient temperature. The radiation stability of the beads was checked in a radiation dose range 10{sup 3}--10{sup 6} Gy (10{sup 5}--10{sup 8} rads). In acidic solutions the stability of PAN binder was proved not to be limited by either chemical or radiation decomposition. PAN binder may thus be used for preparing composite absorbers for treatment of acid wastes from DOE facilities. The same conclusion is valid for alkaline solutions with pH up to 13. In highly alkaline solutions (concentration of NAOH higher than I M) and in the presence of NaNO{sub 3}, the stability of the tested polyacrylonitrile polymer was sufficient for applications not extending over 10 days. Cross-linking of the polymer caused by ionizing radiation was found to have a positive influence on chemical stability. This effect enables a longer period of applicability of PAN-based composite absorbers. Because of the high sorption rate achievable with PAN-based absorbers, the stability achieved is sufficient for most applications in the DOE complex. The chemical stability of binding polymer may also be further improved by testing another, more suitable type of polymer from the broad family of polyacrylonitrile polymers.

Kinetics of plutonium and americium sorption to natural clay

Kinetics of Pu(IV) and Am(III) sorption from natural groundwater to three types of clays were studied at trace concentrations of the elements. Higher K(d) values were determined for sorption of Pu than of Am, and no clear dependence of the K(d) values and the kinetic coefficients on the composition of the clays can be deduced. Kinetic data evaluated by models for six different control processes indicated a sorption mechanism controlled by Pu or Am diffusion in the inert layer on the surface of the clays. Apart from the kinetics of the elements sorption, time-dependent changes in their bonding nature were also studied using a sequential extraction. It was found that Pu(IV) was predominantly associated with amorphous and crystalline Fe oxides as well as natural organic matter sites on the clays, whereas in the case of Am(III) the exchangeable and carbonate sites played the principal role.

Modeling of metal-humate complexation based on the mean molecular weight and charge of humic substances: Application to Eu(III) humate complexes using ion exchange

A general model, the so called Mean Molecular Weight Model (MMWM), of complexation of metal cations (Mez+) with macromolecular polyanions of humic acid (HAp-) is proposed. The model is based on the results of previous studies of the electrophoretic mobility of humate complexes and assumes that the complexation proceeds by consecutive neutralization of the dissociated carboxyl groups of the central polyanion HAp- with Mez+ cations. It reflects the macromolecular character of humic acid, applies molar concentrations of reacting components with equations for stability constants and incorporates also the mean charge of humic macromolecules. The model has been verified with experimental data obtained in the study of complexation of Eu(III) with Aldrich humic acid using ion exchange (Amberlite IR-120), over a broad range of [Eu] to [HA] ratio, at pH 4 and 7.

Kinetics of radioeuropium sorption on Gorleben sand from aqueous solutions and ground water

Kinetics of Eu sorption on sandy sediment from Gorleben, Germany, containing humic substances, was studied by radiotracer method in batch experiments at very low europium concentration (3.4.10-8 mol/l), with the aim to find kinetic parameters suitable for modeling Eu migration in bed of the sediment and to elucidate the mechanism of the sorption. Experiments were evaluated using a new simplified method taking into account simultaneous sorption/desorption of Eu on the walls of sorption vessel. Five kinetic functions were tested, of which that describing diffusion in inert surface layer of sorbent proved most suitable. The effects of pH (3.0-8.8) by addition of Aldrich humic acid (10 mg/l), addition of hydrogencarbonates (5.10-3 mol/l) and preequilibration of the sediment with solution or of Eu with solution were examined. From the results it has been concluded that the kinetics and mechanism of the sorption strongly depend on pH. At pH 4.8 Eu is sorbed mainly as humate complex from the solution of humic acid. The addition of humic acid accelerates the sorption. Carbonate complexes of Eu are the probable forms sorbed at pH 8.8. The presence of humic substances in the slightly alkaline solutions suppresses the rate of the sorption due to slow dissociation of Eu-humate complexes.

Modelling of the sorption of Sr(II) on hydrous zirconium oxide

The amphoteric acid-base behavior of hydrous zirconium oxide (HZO) was investigated by titrating HZO with 0.05M HNO3 and NaOH at constant ionic strength. The sorption of strontium from 0.05M NaNO3 solution was measured as a function of pH. Abrupt increase in sorption was observed at the equilibrium pH of 9. The experimental titration and strontium sorption data on HZO were evaluated using the constant capacitance model (CCM) and diffuse double layer model (DLM). Various model parameters of Surface Complexation Models (SCM) were estimated, numerically, by non-linear regression. Modeling the sorption and speciation of Sr2+ on HZO indicated that the hydrolysis of Sr2+ to lower charged SrOH+ is the pre-requisite for the abrupt sorption behavior at pH 9.

Radiotracer study of sorption of europium on Gorleben sand from aqueous solutions containing humic substances

The sorption of trace europium, as a trivalent actinide homologue, was studied in the system Gorleben sand - aqueous solution with the aim to elucidate its mechanism. Radiotracer method (152/154Eu) and batch experiments were used. Simultaneously, the distribution of humic substances present in, or added to the system was measured. The evaluation of the sorption was complicated by the adsorption of Eu on the walls of polyethylene vials used for the experiments, which was rather high and had to be taken into consideration. It has been found that Eu sorption on Gorleben sand increases from pH 2 to pH 5-7 and then it decreases. The decrease is due to the complexation of Eu with humic substances leached from Gorleben sand at pH >7. The position of the sorption maximum depends on the composition of the solution and on the liquid-to-solid ratio. It is shifted to lower pH values in the presence of added humic acid (HA), which enhances Eu sorption at low pH values and suppresses it at pH values higher than 5. The regions of the enhancing/suppressing effects coincide with the high/low adsorption of HA on Gorleben sand, respectively. The increasing ionic strength (from 0.01 to 0.1) and europium concentration (3.4.10-8 to 9.3.10-7 mol/l) suppress the relative sorption (expressed in %) at low pH values and enhance it at pH>6-8. Addition of carbonates (5.10-3 mol/l) supports Eu sorption at pH>7.5 so that no decrease with pH is observed till pH 9. Alkaline leaching of the sand significantly changes most of the effects found. These results were qualitatively interpreted and conclusions were drawn on the mechanism of the sorption.

Determination of 137Cs and 85Sr transport parameters in fucoidic sand columns and groundwater system

AbstractThe determination is based on the evaluation of experimentally obtained breakthrough curves using the erfc-function. The first method is founded on the assumption of a reversible linear sorption/desorption isotherm of radionuclides on solid phase with constant distribution and retardation coefficients, whereas the second one is based on the assumption of a reversible non-linear sorption/desorption isotherm described with the Freundlich equation, i.e., with non-constant distribution and retardation coefficients. Undisturbed cores of 5 cm in diameter and 10 cm long were embedded in the Eprosin-type cured epoxide resin column. In this study the so-called Cenomanian background groundwater was used as transport medium. The groundwater containing radionuclides was introduced at the bottom of the columns at about 4 mL h−1 constant flow-rate. The results have shown that in the investigated fucoidic sands: (i) the sorption was in principle characterized by linear isotherms and the corresponding retardation coefficients of 137Cs and 85Sr, depending on the type of sample, were approximately 13 or 44 and 5 or 15, respectively; (ii) the desorption was characterized by non-linear isotherms, and the retardation coefficients of the same radionuclides ranged between 23–50 and 5–25, respectively. The values of the hydrodynamic dispersion coefficients of these radionuclides varied between 0.43–1.2 cm2 h−1.

Interaction of 3H+ (as HTO) and 36Cl− (as Na36Cl) with crushed granite and corresponding fracture infill material investigated in column experiments

The transport of 3H+ (as HTO) and 36Cl− (as Na36Cl) was investigated in the dynamic system, i.e., in the columns filled with crushed pure granite and fracture infill of various grain sizes. The aim of column experiments was to determine important transport parameter, such as the retardation, respectively distribution coefficients, Peclet numbers and hydrodynamic dispersion coefficients. Furthermore, the research was focused to quantification of the effect of grain size on migration of studied radionuclides. The experimental breakthrough curves were fitted by a model based on the erfc-function, assuming a linear reversible equilibrium sorption/desorption isotherm, and the above mentioned transport parameters were determined. The results showed that influence of grain size on sorption of 3H+ and 36Cl− was negligible. Retardation and distribution coefficients of both tracers converged to one and zero, respectively, in case of all fractions of crushed granite and infill material. Generally, the presumed ion exclusion of 36Cl in anionic form was proved under given conditions, only very weak one seems to exist in a case of infill material. In principal, both radionuclides behaved as non-sorbing, conservative tracers. On the other hand, the influence of grain size on Peclet numbers value and on dispersion coefficient was observed for both crystalline materials, namely in agreement with theoretical suppositions that the values of Peclet numbers decrease with increasing grain size and values of dispersion coefficient increase.

Retention of selenium and caesium on crystalline rock: the effect of redox conditions and mineralogical composition

Abstract Isotopes of caesium and selenium belong among fission products, being present in spent nuclear fuel (SNF) and high level waste (HLW), and contribute significantly to the risk associated with SNF and HLW disposal in deep geological repositories. The present work is focused on sorption behaviour of Cs and Se species on two types of crystalline rock, granite from Melechov massif (Czech Republic) and Äspö diorite from the underground laboratory Äspö (Sweden). The aim was to compare sorption behaviour of Cs and Se on these rocks under aerobic and anaerobic conditions and determine the influence of redox conditions on their kinetic sorption properties.

Radiotracer study of the kinetics of complexation and decomplexation of Eu(III) with humic acid using ion exchange

The kinetics of complexation (C) and decomplexation (D) reactions between Eu(III) and Aldrich humic acid (HA) was investigated as a function of pH (pH 4, 5, 6, 7 and 8) in the system Eu(III) - HA - Amberlite IR-120(Na) (I = 0.1). The derivation of the kinetic differential equations was based on the reactions of Eu3+ with, so called, strong (HAS) and weak (HAW) carboxylic groups of HA formulated in accordance with the new complexation model.1 The differential equations determining d[EuaHAS]/dt and d[EubHAW]/dt have the classical form applicable for reversible reactions where the forward reaction is the C-reaction and the reverse one is the D-reaction. Kinetic model used for the evaluation of experimental data includes these differential equations and the film diffusion model of sorption of Eu3+ on Amberlite IR-120(Na).